The present invention relates to multicomponent superabsorbent particles, in fiber form, containing at least one acidic water-absorbing resin and at least one basic water-absorbing resin. Each multicomponent superabsorbent fiber has at least one microdomain of the acidic resin in contact with, or in close proximity to, at least one microdomain of the basic resin. The present invention also relates to mixtures containing (a) multicomponent superabsorbent fibers, and (b) particles of an acidic water-absorbing resin, a basic water-absorbing resin, or a mixture thereof.
Water-absorbing resins are widely used in sanitary goods, hygienic goods, wiping cloths, water-retaining agents, dehydrating agents, sludge coagulants, disposable towels and bath mats, disposable door mats, thickening agents, disposable litter mats for pets, condensation-preventing agents, and release control agents for various chemicals. Water-absorbing resins are available in a variety of chemical forms, including substituted and unsubstituted natural and synthetic polymers, such as hydrolysis products of starch acrylonitrile graft polymers, carboxymethylcellulose, crosslinked polyacrylates, sulfonated polystyrenes, hydrolyzed polyacrylamides, polyvinyl alcohols, polyethylene oxides, polyvinylpyrrolidones, and polyacrylonitriles.
Such water-absorbing resins are termed xe2x80x9csuperabsorbent polymers,xe2x80x9d or SAPs, and typically are lightly crosslinked hydrophilic polymers. SAPs are generally discussed in Goldman et al. U.S. Pat. Nos. 5,669,894 and 5,559,335, the disclosures of which are incorporated herein by reference. SAPs can differ in their chemical identity, but all SAPs are capable of absorbing and retaining amounts of aqueous fluids equivalent to many times their own weight, even under moderate pressure. For example, SAPs can absorb one hundred times their own weight, or more, of distilled water. The ability to absorb aqueous fluids under a confining pressure is an important requirement for an SAP used in a hygienic article, such as a diaper.
As used here and hereafter, the term xe2x80x9cSAP particlesxe2x80x9d refers to superabsorbent polymer particles in the dry state, i.e., particles containing from no water up to an amount of water less than the weight of the particles. The terms xe2x80x9cSAP gelxe2x80x9d or xe2x80x9cSAP hydrogelxe2x80x9d refer to a superabsorbent polymer in the hydrated state, i.e., particles that have absorbed at least their weight in water, and typically several times their weight in water. The SAP particles disclosed herein are in fiber form.
The dramatic swelling and absorbent properties of SAPs are attributed to (a) electrostatic repulsion between the charges along the polymer chains, and (b) osmotic pressure of the counter ions. It is known, however, that these absorption properties are drastically reduced in solutions containing electrolytes, such as saline, urine, and blood. The polymers function much less effectively in the presence of such physiologic fluids.
The decreased absorbency of electrolyte-containing liquids is illustrated by the absorption properties of a typical, commercially available SAP, i.e., sodium polyacrylate, in deionized water and in 0.9% by weight sodium chloride (NaCl) solution. The sodium polyacrylate can absorb 146.2 grams (g) of deionized water per gram of SAP (g/g) at 0 psi, 103.8 g of deionized water per gram of polymer at 0.28 psi, and 34.3 g of deionized water per gram of polymer of 0.7 psi. In contrast, the same sodium polyacrylate is capable of absorbing only 43.5 g, 29.7 g, and 24.8 g of 0.9% aqueous NaCl at 0 psi, 0.28 psi, and 0.7 psi, respectively. The absorption capacity of SAPs for body fluids, such as urine or menses, therefore, is dramatically lower than for deionized water because such fluids contain electrolytes. This dramatic decrease in absorption is termed xe2x80x9csalt poisoning.xe2x80x9d
The salt poisoning effect has been explained as follows. Water-absorption and water-retention characteristics of SAPs are attributed to the presence of ionizable functional groups in the polymer structure. The ionizable groups typically are carboxyl groups, a high proportion of which are in the salt form when the polymer is dry, and which undergo dissociation and salvation upon contact with water. In the dissociated state, the polymer chain contains a plurality of functional groups having the same electric charge and, thus, repel one another. This electronic repulsion leads to expansion of the polymer structure, which, in turn, permits further absorption of water molecules. Polymer expansion, however, is limited by the crosslinks in the polymer structure, which are present in a sufficient number to prevent solubilization of the polymer.
It is theorized that the presence of a significant concentration of electrolytes interferes with dissociation of the ionizable functional groups, and leads to the xe2x80x9csalt poisoningxe2x80x9d effect. Dissolved ions, such as sodium and chloride ions, therefore, have two effects on SAP gels. The ions screen the polymer charges and the ions eliminate the osmotic imbalance due to the presence of counter ions inside and outside of the gel. The dissolved ions, therefore, effectively convert an ionic gel into a nonionic gel, and swelling properties are lost.
The most commonly used SAP for absorbing electrolyte-containing liquids, such as urine, is neutralized polyacrylic acid, i.e., containing at least 50%, and up to 100%, neutralized carboxyl groups. Neutralized polyacrylic acid, however, is susceptible to salt poisoning. Therefore, to provide an SAP that is less susceptible to salt poisoning, either an SAP different from neutralized polyacrylic acid must be developed, or the neutralized polyacrylic acid must be modified or treated to at least partially overcome the salt poisoning effect.
The removal of ions from electrolyte-containing solutions is often accomplished using ion exchange resins. In this process, deionization is performed by contacting an electrolyte-containing solution with two different types of ion exchange resins, i.e., an anion exchange resin and a cation exchange resin. The most common deionization procedure uses an acidic resin (i.e., cation exchange) and a basic resin (i.e., anion exchange). The two-step reaction for deionization is illustrated with respect to the desalinization of water as follows:
NaCl+Rxe2x80x94SO3Hxe2x86x92Rxe2x80x94SO3Na+HCl
HCl+Rxe2x80x94N(CH3)3OHxe2x86x92Rxe2x80x94N(CH3)3Cl+H2O.
The acidic resin (Rxe2x80x94SO3H) removes the sodium ion; and the basic resin (Rxe2x80x94N(CH3)3OH) removes the chloride ions. This ion exchange reaction, therefore, produces water as sodium chloride is adsorbed onto the resins. The resins used in ion exchange do not absorb significant amounts of water.
The most efficient ion exchange occurs when strong acid and strong base resins are employed. However, weak acid and weak base resins also can be used to deionize saline solutions. The efficiency of various combinations of acid and base exchange resins are as follows:
Strong acidxe2x80x94strong base (most efficient)
Weak acidxe2x80x94strong base
Strong acidxe2x80x94weak base
Weak acidxe2x80x94weak base (least efficient).
The weak acid/weak base resin combination requires that a xe2x80x9cmixed bedxe2x80x9d configuration be used to obtain deionization. The strong acid/strong base resin combination does not necessarily require a mixed bed configuration to deionize water. Deionization also can be achieved by sequentially passing the electrolyte-containing solution through a strong acid resin and strong base resin.
A xe2x80x9cmixed bedxe2x80x9d configuration of the prior art is a physical mixture of an acid ion exchange resin and a base ion exchange resin in an ion exchange column, as disclosed in Battaerd U.S. Pat. No. 3,716,481. Other patents directed to ion exchange resins having one ion exchange resin imbedded in a second ion exchange resin are Hatch U.S. Pat. No. 3,957,698, Wade et al. U.S. Pat. No. 4,139,499, Eppinger et al. U.S. Pat. No. 4,229,545, and Pilkington U.S. Pat. No. 4,378,439. Composite ion exchange resins also are disclosed in Hatch U.S. Pat. Nos. 3,041,092 and 3,332,890, and Weiss U.S. Pat. No. 3,645,922.
The above patents are directed to nonswelling resins that can be used to remove ions from aqueous fluids, and thereby provide purified water. Ion exchange resins used for water purification must not absorb significant amounts of water because resin swelling resulting from absorption can lead to bursting of the ion exchange containment column.
Ion exchange resins or fibers also have been disclosed for use in absorbent personal care devices (e.g., diapers) to control the pH of fluids that reach the skin, as set forth in Berg et al., U.S. Pat. No. 4,685,909. The ion exchange resin is used in this application to reduce diaper rash, but the ion exchange resin is not significantly water absorbent and, therefore, does not improve the absorption and retention properties of the diaper.
Ion exchange resins having a composite particle containing acid and base ion exchange particles embedded together in a matrix resin, or having acid and base ion exchange particles adjacent to one another in a particle that is free of a matrix resin are disclosed in B. A. Bolto et al., J. Polymer Sci. :Symposium No. 55, John Wiley and Sons, Inc. (1976), pages 87-94. The Bolto et al. publication is directed to improving the reaction rates of ion exchange resins for water purification and does not utilize resins that absorb substantial amounts of water.
Other investigators have attempted to counteract the salt poisoning effect and thereby improve the performance of SAPs with respect to absorbing electrolyte-containing liquids, such as menses and urine. For example, Tanaka et al. U.S. Pat. No. 5,274,018 discloses an SAP composition comprising a swellable hydrophilic polymer, such as polyacrylic acid, and an amount of an ionizable surfactant sufficient to form at least a monolayer of surfactant on the polymer. In another embodiment, a cationic gel, such as a gel containing quaternized ammonium groups and in the hydroxide (i.e., OH) form, is admixed with an anionic gel (i.e., a polyacrylic acid) to remove electrolytes from the solution by ion exchange. Quaternized ammonium groups in the hydroxide form are very difficult and time-consuming to manufacture, thereby limiting the practical use of such cationic gels.
Wong U.S. Pat. No. 4,818,598 discloses the addition of a fibrous anion exchange material, such as DEAE (diethylaminoethyl) cellulose, to a hydrogel, such as a polyacrylate, to improve absorption properties. The ion exchange resin xe2x80x9cpretreatsxe2x80x9d the saline solution (e.g., urine) as the solution flows through an absorbent structure (e.g., a diaper). This pretreatment removes a portion of the salt from the saline. The conventional SAP present in the absorbent structure then absorbs the treated saline more efficiently than untreated saline. The ion exchange resin, per se, does not absorb the saline solution, but merely helps overcome the xe2x80x9csalt poisoningxe2x80x9d effect.
WO 96/17681 discloses admixing discrete anionic SAP particles, such as polyacrylic acid, with discrete polysaccharide-based cationic SAP particles to overcome the salt poisoning effect. Similarly, WO 96/15163 discloses combining a cationic SAP having at least 20% of the functional groups in a basic (i.e., OH) form with a cationic exchange resin, i.e., a nonswelling ion exchange resin, having at least 50% of the functional groups in the acid form. WO 96/15180 discloses an absorbent material comprising an anionic SAP, e.g., a polyacrylic acid and an anion exchange resin, i.e., a nonswelling ion exchange resin.
SAP particles in fiber form are known. For example, Allen U.S. Pat. No. 5,147,956 and Allen et al. U.S. Pat. Nos. 4,962,172; 4,861,539; and 4,280,079 disclose absorbent products and their method of manufacture. Farrar et al. U.S. Pat. No. 4,997,714 also discloses absorbent products in a fiber form, and their method of manufacture. Additional patents include Morgan U.S. Pat. No. 3,867,499, Funk U.S. Pat. No. 4,913,869, and Tai et al. U.S. Pat. No. 5,667,743. GB 2,269,602 discloses a wet-laid nonwoven fabric comprising a blend of SAP fibers and a less absorbing fiber, like woodpulp. European Patent Application 0 425 269 discloses a melt spun fiber containing a conventional synthetic material and an SAP. WO 98/24832 discloses an absorbent composition containing an acidic and basic material. The absorbent composition can be in a fiber form. Further patents directed to fibers include WO 96/JP651, WO 97/43480, and Hills U.S. Pat. No. 5,162,074.
Various references disclose combinations that attempt to overcome the salt poisoning effect. However, the references do not teach SAP fibers having the improved fluid absorption and retention properties, or absorption kinetics, demonstrated by the fibers of the present invention, which comprise at least one microdomain of an acidic resin in contact, or in close proximity, with at least one microdomain of a basic resin. These references also do not teach a mixture of resin particles wherein one component of the mixture is fibers of a multicomponent SAP.
The present invention, therefore, is directed to discrete SAP fibers that exhibit exceptional water absorption and retention properties, especially with respect to electrolyte-containing liquids, and thereby overcome the salt poisoning effect. In addition, the discrete SAP fibers have an ability to absorb liquids quickly, demonstrate good fluid permeability and conductivity into and through the SAP fiber, and have a high gel strength such that the hydrogel formed from the SAP fibers does not deform or flow under an applied stress or pressure, when used alone or in a mixture with other water-absorbing resins.
The present invention is directed to multicomponent SAPs, in fiber form, comprising at least one acidic water-absorbing resin, such as a polyacrylic acid, and at least one basic water-absorbing resin, such as a poly(vinylamine), a polyethyleneimine, or a poly(dialkylaminoalkyl acrylamide) or a poly(dialkylaminoalkyl methacrylamide), hereafter collectively referred to as poly(dialkylaminoalkyl(meth)acrylamides).
More particularly, the present invention is directed to multicomponent SAP fibers containing at least one discrete microdomain of at least one acidic water-absorbing resin in contact with, or in close proximity to, at least one microdomain of at least one basic water-absorbing resin. The acidic resin can be a strong or a weak acidic resin. Similarly, the basic resin can be a strong or a weak basic resin.
A preferred SAP contains one or more microdomains of at least one weak acidic resin and one or more microdomains of at least one weak basic resin. The properties demonstrated by such preferred multicomponent SAP particles are unexpected because, in ion exchange applications, the combination of a weak acid and a weak base is the least effective of any combination of a strong or weak acid ion exchange resin with a strong or weak basic ion exchange resin.
The multicomponent SAP fibers can contain a plurality of microdomains of the acidic water-absorbing resin and/or the basic water-absorbing resin dispersed throughout the particle. Alternatively, the multicomponent SAP fibers can be in the form of a core and sheath, wherein the core is a microdomain of a first water-absorbing resin and the sheath is a microdomain of a second water-absorbing resin. The multicomponent SAP fibers also can be in the form of a fiber of an acidic water-absorbing resin and a fiber of a basic water-absorbing resin that are twisted together in the form of a braid or rope.
Accordingly, one aspect of the present invention is to provide SAP fibers that have a high absorption rate, have good permeability and gel strength, overcome the salt poisoning effect, and demonstrate an improved ability to absorb and retain electrolyte-containing liquids, such as saline, blood, urine, and menses. The present SAP fibers contain discrete microdomains of acidic and basic resin, and during hydration, the fibers resist coalescence but remain fluid permeable.
Another aspect of the present invention is to provide an SAP having improved absorption and retention properties compared to a conventional SAP, such as sodium polyacrylate. The present multicomponent SAP fibers are produced by any method that positions a microdomain of an acidic water-absorbing resin in contact with, or in close proximity to, a microdomain of a basic water-absorbing resin to provide a discrete particle. Such SAP particles demonstrate improved absorption and retention properties, and permeability through and between particles compared to SAP compositions comprising a simple admixture of acidic resin particles and basic resin particles.
In one embodiment, the SAP fibers are produced by coextruding an acidic water-absorbing hydrogel and a basic water-absorbing hydrogel to provide multicomponent SAP fibers having a plurality of discrete microdomains of an acidic resin and a basic resin dispersed throughout the particle. In another embodiment, the present multicomponent SAP fibers can be prepared by admixing dry particles of a basic resin with a hydrogel of an acidic resin, then extruding the resulting mixture to form multicomponent SAP fibers having microdomains of a basic resin dispersed throughout a continuous phase of an acidic resin. Alternatively, dry acidic resin particles can be admixed with a basic resin hydrogel, followed by extruding the resulting mixture to form multicomponent SAP fibers having microdomains of an acidic resin dispersed in a continuous phase of a basic resin.
In addition, a multicomponent SAP fiber containing microdomains of an acidic resin and a basic resin dispersed in a continuous phase of a matrix resin can be prepared by adding dry particles of the acidic resin and dry particles of the basic resin to a hydrogel of the matrix hydrogel, then extruding.
In other embodiments, the acidic and basic water-absorbing hydrogels are coextruded, or spun, to form a fiber having a core-sheath configuration. Alternatively, the acidic and basic water-absorbing hydrogels are extruded, or spun, individually, then twisted together, in the form of a braid, to provide a multicomponent SAP fiber.
In accordance with yet another important aspect of the present invention, the acidic and basic resins are lightly crosslinked, such as with a suitable polyfunctional vinyl polymer. In preferred embodiments, the acidic resin, the basic resin, and/or the entire multicomponent SAP fiber are surface treated or annealed to further improve water absorption and retention properties, especially under a load.
Yet another important feature of the present invention is to provide an SAP fiber containing at least one microdomain of a weak acidic water-absorbing resin in contact with at least one microdomain of a weak basic water-absorbing resin.
An example of a weak acidic resin is polyacrylic acid having 0% to 25% neutralized carboxylic acid groups (i.e., DN=0 to DN=25). Examples of weak basic water-absorbing resins are a poly(vinylamine), a polyethylenimine, and a poly(dialkylaminoalkyl (meth) acrylamide) prepared from a monomer either having the general structure formula (I) 
or the ester analog of (I) having the general structure formula (II) 
wherein R1 and R2, independently, are selected from the group consisting of hydrogen and methyl, Y is a divalent straight chain or branched organic radical having 1 to 8 carbon atoms, and R3 and R41 independently, are alkyl radicals having 1 to 4 carbon atoms. Examples of a strong basic water-absorbing resin are poly(vinylguanidine) and poly(allylguanidine).
Yet another aspect of the present invention is to provide an improved SAP material comprising a combination containing (a) multicomponent SAP fibers, and (b) particles of a second water-absorbing resin selected from the group consisting of an acidic water-absorbing resin, a basic water-absorbing resin, and a mixture thereof. The combination contains about 10% to about 90%, by weight, multicomponent SAP fibers and about 10% to about 90%, by weight, particles of the second water-absorbing resin.
Another important aspect of the present invention is to provide a method of continuously producing core-sheath multicomponent SAP fibers. In one embodiment, a poly(vinylamine) core is prepared using a wet spinning method, which then is immediately directed to a solution containing poly(acrylic acid) and a crosslinker. The freshly spun poly(vinylamine) fiber, therefore, has a sheath of poly(acrylic acid) applied thereto.
Still another aspect of the present invention is to provide diapers having a core comprising multicomponent SAP fibers or an SAP material of the present invention. Other articles that can contain the multicomponent SAP fibers or an SAP material of the present invention include catamenial devices, adult incontinence products, and devices for absorbing saline and other ion-containing fluids.
These and other aspects and advantages of the present invention will become apparent from the following detailed description of the preferred embodiments.
FIG. 1 is a cross-sectional view of a water-absorbing fiber containing microdomains of a first resin dispersed in a continuous phase of a second resin;
FIG. 2 is a cross-sectional view of a water-absorbing particle containing microdomains of a first resin and microdomains of a second resin dispersed throughout the particle;
FIGS. 3A and 3B are cross-sectional views of a water-absorbing fiber having a core microdomain of a first resin surrounded by a sheath microdomain of a second resin;
FIGS. 4A and 4B are cross-sectional views of water-absorbing fibers having a microdomain of a first resin in contact with a microdomain of a second resin;
FIGS. 5A and 5B are schematic diagrams of a water-absorbing fiber having individual fibers of a first and a second water-absorbing resin twisted together to form a rope;
FIG. 6 contains plots of absorbance (in grams of synthetic urine per gram of multicomponent SAP granules) vs. annealing temperature for a one-hour annealing step;
FIG. 7 contains a plot of absorbance (in grams of synthetic urine per gram of multicomponent SAP granules) vs. time for an annealing step performed at 125xc2x0 C.;
FIG. 8 is a schematic illustration of a dry spinning apparatus;
FIG. 9 is a schematic illustration of a wet spinning apparatus;
FIG. 10 contains plots of AUL (0.28 psi) (g/g) vs. time for rate of absorption of twisted SAP fibers cured at 125xc2x0 C. for 20 mins.; and
FIGS. 11 and 12 are scanning electron micrographs of the multicomponent SAP fibers of Example 7.